CN113908109A - Propolis anti-allergy toothpaste and preparation method thereof - Google Patents

Abstract

The invention discloses propolis anti-allergy toothpaste and a preparation method thereof, and the components of the propolis anti-allergy toothpaste comprise 5-10 parts by weight of an anti-allergy agent, 2-5 parts by weight of a stabilizer, 2-5 parts by weight of a whitening agent, 0.5-1 part by weight of a sweetening agent, 1-3 parts by weight of a remineralizing agent, 15-25 parts by weight of a friction agent, 40-60 parts by weight of a humectant, 0.1-2 parts by weight of a thickening agent, 1-2 parts by weight of a foaming agent, 0.1-2 parts by weight of a spice and 10-25 parts by weight of water. The propolis anti-allergy toothpaste has better whitening and anti-allergy performances, and can comprehensively protect teeth and oral health.

Description

Propolis anti-allergy toothpaste and preparation method thereof

Technical Field

The invention belongs to the technical field of oral cleaning products, and particularly relates to propolis anti-allergy toothpaste and a preparation method thereof.

Background

Teeth are important functional organs of human body, and normal teeth are glossy and semitransparent ivory colors. However, the stained teeth caused by various factors greatly affect the beauty of the teeth, bring social inconvenience to people and have adverse psychological effects. Clinically, many doctors and oral care product researchers are dedicated to study whitening of teeth. In addition, dentinal hypersensitivity is a common oral disease, and a recent system review reports that 65 studies meeting study inclusion and exclusion criteria have an average prevalence of 33.5%, which rises to 43.9% when analyzing data from studies limited to young adults. In a healthy mouth, this occurs when dentin is typically exposed by tooth wear or gum recession and dentinal tubules are opened to allow patency from the tooth surface to the pulp. When the dentinal tubules are exposed to stimuli such as cold air or water, pressure or permeability, the fluid within the dentinal tubules transmits the stimuli to the pulp nerves, resulting in a transient, intense pain response. Although pain is usually transient, it can also be severe and have a significant negative impact on the quality of life. Therefore, there is a need for a toothpaste having whitening and anti-sensitivity properties.

Propolis is a colloidal substance obtained by collecting resin from plant buds, barks, etc. by bees, mixing with glandular secretion of bees such as lingual gland and wax gland, and processing and transforming with bees. In foreign countries, propolis is known as "purple gold". Propolis is a natural antibacterial agent with antimicrobial effect, and has certain inhibiting effect on bacteria and fungi.

CN 112618415A discloses an ice white toothpaste and a preparation method thereof, wherein the ice white toothpaste comprises the following components by weight: 15-25 parts of glycerol, 40-45 parts of calcium hydrophosphate, 0.8-1.2 parts of glucose oxidase, 1-2 parts of xanthan gum, 2-4 parts of sodium lauroyl sarcosinate, 0.1-0.5 part of menthol, 0.2-0.5 part of sodium benzoate, 0.3-0.5 part of sodium pyrophosphate, 16.3-37.6 parts of deionized water and 3-5 parts of polyethylene glycol 400, and the prepared toothpaste can whiten teeth of a user in a short time, enables the teeth to have luster, does not damage the teeth and is used for exogenous periodontal diseases; the toothpaste has good effects on exogenous tooth staining and mild endogenous tooth staining, can safely and effectively remove tooth stain and dental plaque without damaging enamel or stimulating gum, and can efficiently whiten teeth in a short time; but has no anti-allergy effect.

CN107412138A discloses a Brazilian green propolis toothpaste, which is prepared from sorbitol, calcium hydrogen phosphate, hydrated silica, deionized water, propylene glycol, sodium lauryl sulfate, Brazilian green propolis, crosslinked carboxymethyl cellulose, essence, sodium pyrophosphate, saccharin sodium, carboxymethyl hydroxypropyl guar gum, methyl hydroxybenzoate, paeonol and cooling agent. The Brazilian green propolis is propolis stock solution, water-soluble flavone and beeswax which are obtained by carrying out non-critical extraction on the Brazilian green propolis. The toothpaste body is fine and smooth, can play roles in oral health care, oral ulcer prevention, oral odor elimination and the like, and has no toxic or side effect after long-term use; but has no anti-allergy effect.

Disclosure of Invention

The invention provides propolis anti-allergy toothpaste, wherein the propolis extract obtained by alcohol extraction is added in the formula, and the propolis anti-allergy toothpaste does not contain beeswax, so that the anti-allergy and antibacterial effects of the toothpaste are effectively improved; and the stability of the toothpaste is effectively improved by adding the anion graft modified chitosan.

The inventor finds that the main source of the substances playing the antibacterial action in the propolis is polyphenol. Therefore, the invention adopts an alcohol extraction method to prepare the propolis extract. The compatibility of polyphenol and ketone substances in the propolis extract with toothpaste is poor, and the tolerance of common thickening agents in the toothpaste, such as polyphenol and ketone substances such as sodium carboxymethyl cellulose, sodium hydroxyethyl cellulose, nonionic guar gum, xanthan gum, carrageenan, sodium alginate and the like, is poor, so that the internal structure is easily damaged by influence; resulting in poor stability of the paste and easy separation. According to the invention, the stabilizer-chitosan is further modified to prepare the anion graft modified chitosan, so that the problem of paste instability caused by the addition of the alcohol extracted propolis extract can be effectively solved.

The technical scheme of the invention is as follows:

an antiallergic toothpaste contains propolis extract.

Preferably, the propolis anti-allergy toothpaste comprises 5-10 parts by weight of propolis extract, 5-10 parts by weight of an anti-allergy agent, 2-5 parts by weight of a stabilizer, 2-5 parts by weight of a whitening agent, 0.5-1 part by weight of a sweetening agent, 1-3 parts by weight of a remineralizing agent, 15-25 parts by weight of a friction agent, 40-60 parts by weight of a humectant, 0.1-2 parts by weight of a thickener, 1-2 parts by weight of a foaming agent, 0.1-2 parts by weight of a spice and 10-25 parts by weight of water; the stabilizer is at least one of carboxymethyl chitosan, silk peptide, carboxymethyl chitosan/silk peptide hydrogel and anion graft modified chitosan.

Preferably, the preparation method of the propolis extract comprises the following steps: mixing propolis and ethanol water solution uniformly, oscillating and leaching at room temperature, filtering to remove beeswax, and freeze drying to obtain the propolis extract.

Further preferably, the preparation method of the propolis extract comprises the following steps: according to the mass ratio of 1: (2-6) uniformly mixing propolis with an ethanol water solution, oscillating at 100-200 rpm at room temperature for 1-3 days, filtering to remove beeswax, and freeze-drying to obtain the propolis extract; the concentration of the ethanol water solution is 25-70 wt%.

Preferably, the anti-allergic agent consists of potassium nitrate and strontium chloride.

The whitening agent is one or the combination of two or more of sodium pyrophosphate, sodium phytate, titanium dioxide, perlite powder and zinc oxide.

Preferably, the sweetener is one or a combination of two or more of stevioside, saccharin sodium, xylitol, sucralose and dipotassium glycyrrhizinate.

Preferably, the remineralizing agent is hydroxyapatite.

Preferably, the friction agent is one or a combination of two or more of hydrated silicon dioxide, calcium hydrogen phosphate, calcium carbonate and aluminum hydroxide.

Preferably, the humectant is one or a combination of two or more of glycerol, sorbitol, propylene glycol, diethylene glycol and ethylene glycol.

Preferably, the thickener is one or a combination of two or more of carboxymethylcellulose sodium, hydroxyethyl cellulose sodium, nonionic guar gum, xanthan gum, carrageenan and sodium alginate.

Preferably, the foaming agent is one or a combination of two or more of sodium dodecyl sulfate, sodium lauroyl sarcosinate, sodium lauroyl methyl taurate, sodium lauryl sulfate, cocamidopropyl betaine and sodium cocoyl glycinate.

The carboxymethyl chitosan is one of the derivatives of chitosan, is a natural amphoteric polyelectrolyte polysaccharide, not only retains the characteristics of high biocompatibility, antibacterial property, degradability and the like of the chitosan, but also has various characteristics of water solubility, pH sensitivity and the like, so that the physicochemical properties of the chitosan are optimized and improved, and the defects of the chitosan in production and application are overcome. The silk peptide is a degradation product of silk protein, the components of the silk peptide are similar to proteins such as keratin, collagen, elastin and the like, and the silk peptide has a good absorption mechanism and has physiological effects of reducing blood sugar and cholesterol, resisting oxidation and resisting aging. In addition, the silk peptide has many hydrophilic groups (such as hydroxyl, carboxyl, amino, etc.) on the molecular structure and on the surface of the molecular three-dimensional structure. Because carboxymethyl chitosan and silk peptide have a large amount of hydroxyl and carboxyl, the carboxymethyl chitosan and the silk peptide can generate certain crosslinking reaction in a liquid phase environment, and a network structure can be formed by the crosslinking reaction of the carboxymethyl chitosan and the silk peptide, so that the stability of the anti-allergic agent is improved.

Genipin is the product of geniposide which is the active ingredient in eucommia ulmoides oliv of Chinese medicine and is hydrolyzed by beta-glucuronidase. Genipin belongs to iridoid, and has remarkable effects in resisting inflammation, treating endocrine system and tumor. The genipin molecule has a plurality of active groups such as hydroxyl, carboxyl and the like, and can react with free amino. Therefore, the carboxymethyl chitosan and the silk peptide rich in hydroxyl and amino can be modified by the crosslinking reaction with genipin molecules, so that a network structure is formed inside to improve the stability of the carboxymethyl chitosan and the silk peptide. The hydrogel prepared by the crosslinking reaction of the carboxymethyl chitosan, the silk peptide and the genipin is more beneficial to improving the performance of the stabilizer.

Preferably, the preparation method of the carboxymethyl chitosan/silk peptide hydrogel comprises the following steps: dissolving carboxymethyl chitosan and silk peptide in water to form a solution a; dissolving genipin in water to form a solution b; and mixing the solution a and the solution b for crosslinking reaction for 24-36 h, washing with water for three times, and freeze-drying at-55 to-45 ℃ for 24-36 h to obtain the carboxymethyl chitosan/silk peptide composite hydrogel.

More preferably, the preparation method of the carboxymethyl chitosan/silk peptide hydrogel comprises the following steps: dissolving 0.5-3 parts by weight of carboxymethyl chitosan and 1-5 parts by weight of silk peptide in 50-150 parts by weight of water at the temperature of 20-25 ℃ and the rotating speed of 300-500 r/min to form a solution a; dissolving 0.1-0.5 weight part of genipin in 50-150 weight parts of water at the temperature of 20-25 ℃ at the rotating speed of 300-500 r/min to form a solution b; and mixing the solution a and the solution b, carrying out crosslinking reaction for 24-36 h at 30-50 ℃, washing with water for three times, and then carrying out freeze drying for 24-36 h at-55 to-45 ℃ to obtain the carboxymethyl chitosan/silk peptide hydrogel.

More preferably, in some embodiments the stabilizer is carboxymethyl chitosan/silk peptide hydrogel to anionic graft-modified chitosan in a mass ratio of 1: (0.3 to 1).

Preferably, the preparation method of the anion graft modified chitosan comprises the following steps: adding chitosan into distilled water, stirring and dispersing uniformly; dropwise adding glacial acetic acid, stirring and mixing uniformly; adding acrylamide and 2-acrylamido-2-methyl-1-propanesulfonic acid, and stirring and mixing uniformly; dropwise adding ammonium ceric nitrate aqueous solution under nitrogen atmosphere, stirring and mixing uniformly, standing for 1-3 h at 20-40 ℃, then aging for 10-24 h at room temperature, centrifuging to take out lower-layer gel, washing with ethanol, freeze-drying, and grinding into powder to obtain the anion graft modified chitosan.

More preferably, the preparation method of the anion graft modified chitosan comprises the following steps: adding 0.8-1.5 g of chitosan into 20-50 mL of distilled water, and uniformly stirring and dispersing; dropwise adding 0.3-0.8 mL of glacial acetic acid, and continuously stirring and uniformly mixing; adding 7-10 g of acrylamide and 1-2 g of 2-acrylamido-2-methyl-1-propanesulfonic acid, and uniformly stirring and mixing; dropwise adding 1-3 mL of 0.05-0.3 mol/L ammonium ceric nitrate aqueous solution under nitrogen atmosphere, stirring and mixing uniformly, standing for 1-3 h at 20-40 ℃, aging for 10-24 h at room temperature, centrifuging to take the lower layer gel, washing with ethanol, freeze-drying, and grinding into powder to obtain the anion graft modified chitosan.

Preferably, the spice is one or the combination of two or more of menthol, peppermint oil, eucalyptus oil, sweet orange oil and lemon oil.

The invention also provides a preparation method of the propolis anti-allergy toothpaste, which comprises the following steps:

s1, weighing the raw materials according to the formula; dissolving an anti-allergic agent, a stabilizing agent, a whitening agent and a sweetening agent into partial water under stirring at 50-100 r/min to form a solution I;

s2, mixing the remineralizing agent, the friction agent and the thickening agent under stirring at 50-100 r/min to form a mixed system II;

s3, mixing the humectant and the rest water under stirring at 50-100 r/min to form a system III, adding the solution I obtained in the step S1 into the system III, vacuumizing to-0.05-0.1 Mpa, and stirring at 50-100 r/min to form a system IV; pumping the mixed system II into the system IV, and homogenizing for 10-20 min at the rotation speed of 8000-10000 r/min and the vacuum degree of-0.05-0.085 Mpa to obtain a system V;

s4, absorbing the foaming agent and the spice into the system V of the step S3, and homogenizing for 10-20 min at the vacuum degree of-0.05-0.085 Mpa and the rotating speed of 8000-10000 r/min; then degassing until the vacuum degree is-0.95 to-0.1 Mpa, and obtaining the propolis anti-allergy toothpaste.

Preferably, the amount of the part of water for dissolution in step S1 is 40 to 60% by mass of the total water.

The invention has the following beneficial effects:

(1) the propolis anti-allergy toothpaste prepared by the invention has the effects of diminishing inflammation, whitening, resisting allergy and the like, the tooth state is obviously improved after eight weeks by using the toothpaste, and the teeth and the oral health can be comprehensively protected.

(2) The whitening and anti-allergy components are stabilized through the carboxymethyl chitosan/silk peptide hydrogel, so that the contact between the effective substances and teeth is closer, and the factors act together to ensure that the toothpaste prepared by the invention has better whitening and anti-allergy performance.

(3) The propolis extract extracted by alcohol is added, so that the beeswax is not contained, and the anti-allergy and antibacterial effects of the toothpaste are effectively improved; and the stability of the toothpaste is effectively improved by adding the anion graft modified chitosan.

Detailed Description

Materials used in the examples are presented:

silk peptide, molecular weight 300 ~ 5000, procures in peptide biotechnology (xi' an) limited company.

Titanium dioxide, with a particle size of 2-10 μm, was purchased from Shanghai Hu titanium dioxide chemical products, Inc.

The nonionic guar gum is a high-molecular derivative with higher hydroxypropyl substitution degree produced by taking natural guar gum as a raw material, can effectively reduce the stimulation of a detergent to skin when being used in daily chemical products, can be used as a thickening agent, a stabilizing agent and a suspending agent in a formula system of the daily chemical products, and is purchased from Hebei Hehaixi chemical industry Co.

EXAMPLE 1 whitening anti-allergy silk peptide toothpaste

The whitening and anti-allergy silk peptide toothpaste comprises the following raw materials by mass:

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 50g of carboxymethyl chitosan;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine;

spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1 putting 70g of potassium nitrate, 30g of strontium chloride, 50g of carboxymethyl chitosan, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the components in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; then degassing to the vacuum degree of-0.1 Mpa, and obtaining the whitening anti-hypersensitive peptide toothpaste.

EXAMPLE 2A whitening anti-allergy peptide toothpaste

The whitening and anti-allergy silk peptide toothpaste comprises the following raw materials by mass:

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 50g of silk peptide;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine

Spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1 putting 70g of potassium nitrate, 30g of strontium chloride, 50g of silk peptide, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the components in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; then degassing to the vacuum degree of-0.1 Mpa, and obtaining the whitening anti-hypersensitive peptide toothpaste.

EXAMPLE 3 whitening anti-allergy silk peptide toothpaste

The whitening and anti-allergy silk peptide toothpaste comprises the following raw materials by mass:

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 15g of carboxymethyl chitosan and 35g of silk peptide;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine

Spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1 putting 70g of potassium nitrate, 30g of strontium chloride, 15g of carboxymethyl chitosan, 35g of silk peptide, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the materials in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; then degassing to the vacuum degree of-0.1 Mpa, and obtaining the whitening anti-hypersensitive peptide toothpaste.

EXAMPLE 4 whitening anti-allergy silk peptide toothpaste

The whitening and anti-allergy silk peptide toothpaste comprises the following raw materials by mass:

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 50g of carboxymethyl chitosan/silk peptide hydrogel;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine

Spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1, putting 70g of potassium nitrate, 30g of strontium chloride, 50g of carboxymethyl chitosan/silk peptide hydrogel, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the materials in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; degassing to vacuum degree of-0.1 Mpa, and collecting the toothpaste to obtain whitening anti-allergy peptide toothpaste;

the preparation method of the carboxymethyl chitosan/silk peptide hydrogel in the step S1 comprises the following steps: dissolving 1.5g of carboxymethyl chitosan and 3.5g of silk peptide in 100g of water at the temperature of 25 ℃ and the rotating speed of 300r/min to form a solution a; 0.2g of genipin is dissolved in 100g of water at the temperature of 25 ℃ and the rotating speed of 300r/min to form a solution b; and mixing the solution a and the solution b, carrying out crosslinking reaction for 24h at 40 ℃, washing with water for three times, and then carrying out freeze drying for 36h at-55 ℃ to obtain the carboxymethyl chitosan/silk peptide composite hydrogel.

Example 5

The propolis anti-allergy toothpaste comprises the following raw materials by mass:

60g of propolis extract;

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 30g of carboxymethyl chitosan/silk peptide hydrogel and 20g of anion graft modified chitosan;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine

Spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1, putting 70g of potassium nitrate, 30g of strontium chloride, 50g of carboxymethyl chitosan/silk peptide hydrogel, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the materials in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; degassing to vacuum degree of-0.1 Mpa, and collecting the paste to obtain propolis antiallergic toothpaste;

the preparation method of the carboxymethyl chitosan/silk peptide hydrogel described in step S1 is the same as that in example 4, and is not repeated here.

The preparation method of the anion graft modified chitosan comprises the following steps: adding 1.2g of chitosan into 30mL of distilled water, and stirring and dispersing uniformly at the rotating speed of 200 rpm; 0.6mL of glacial acetic acid is added dropwise and continuously stirred and mixed for 5 min; adding 8.4g of acrylamide and 1.26g of 2-acrylamido-2-methyl-1-propanesulfonic acid, stirring and mixing for 5 min; dropwise adding 2mL of 0.1mol/L ammonium ceric nitrate aqueous solution under nitrogen atmosphere, stirring and mixing uniformly, standing at 35 ℃ for 2h, aging at room temperature for 12h, centrifuging at 5000rpm for 5min, taking the lower layer gel, washing with ethanol for 5 times, freeze-drying, and grinding into powder to obtain the anion graft modified chitosan.

The preparation method of the propolis extract comprises the following steps: according to the mass ratio of 1: 4 mixing propolis with 50 wt% ethanol water solution uniformly, shaking at 150rpm at room temperature for 2 days, filtering to remove beeswax, and freeze drying to obtain the propolis extract.

Comparative example 1

The propolis anti-allergy toothpaste comprises the following raw materials by mass:

60g of propolis extract;

anti-allergic agent: 70g of potassium nitrate and 30g of strontium chloride;

a stabilizer: 50g of carboxymethyl chitosan/silk peptide hydrogel;

whitening agent: 10g of titanium dioxide and 30g of sodium pyrophosphate;

a sweetening agent: 4g of xylitol and 6g of stevioside;

remineralizing agent: 20g of hydroxyapatite;

a friction agent: 200g of hydrated silicon dioxide and 50g of calcium carbonate;

humectant: 180g of glycerol and 420g of sorbitol;

thickening agent: 4g of sodium carboxymethyl cellulose, 16g of nonionic guar gum;

foaming agent: 12g of sodium lauroyl sarcosinate and 8g of cocamidopropyl betaine

Spice: 10g of menthol;

water: 180 g.

The preparation method of the whitening anti-allergy silk peptide toothpaste comprises the following steps:

s1, putting 70g of potassium nitrate, 30g of strontium chloride, 50g of carboxymethyl chitosan/silk peptide hydrogel, 10g of titanium dioxide, 30g of sodium pyrophosphate, 4g of xylitol, 6g of stevioside and 100g of water into a liquid material tank, and dissolving the materials in the liquid material tank under stirring at 60r/min to form a solution I;

s2, placing 20g of hydroxyapatite, 200g of hydrated silicon dioxide, 50g of calcium carbonate, 4g of sodium hydroxymethyl cellulose and 16g of nonionic guar gum into a powder tank, and mixing under stirring at 60r/min to form a mixed system II;

s3, putting 180g of glycerol, 420g of sorbitol and the rest 80g of water into a paste making tank, and mixing under stirring at 60r/min to form a system III; adding the solution I in the liquid tank in the step S1 into a system III, then vacuumizing the paste preparation tank to-0.05 Mpa, and stirring at 60r/min to form a system IV; pumping the mixed system II in the powder tank obtained in the step S2 into the system IV, and homogenizing at a rotation speed of 8000r/min and a vacuum degree of-0.05 Mpa for 10min to obtain a system V;

s4, sucking 12g of sodium lauroyl sarcosinate, 8g of cocamidopropyl betaine and 10g of menthol into the system V of the step S3, and homogenizing for 10min under the vacuum degree of-0.05 Mpa and the rotating speed of 8000 r/min; degassing to vacuum degree of-0.1 Mpa, and collecting the toothpaste to obtain whitening anti-allergy peptide toothpaste;

the preparation method of the carboxymethyl chitosan/silk peptide hydrogel is the same as that of example 4, and the details are not repeated herein.

The preparation method of the propolis extract is the same as that of example 5, and is not repeated herein.

Test example 1 foaming Performance test of toothpaste

The test refers to the study on the properties and applications of acyl amino acid surfactants in the university of Dalian Industrial science, Zijuan.

The foaming performance test method of the toothpaste comprises the following steps: respectively dissolving 10g of the toothpaste prepared in the examples 1-4 in 100g of deionized water at 25 ℃, setting three groups in parallel for each example, then respectively taking 20mL of the obtained toothpaste solution, transferring the toothpaste solution into a 500mL measuring cylinder with a plug, plugging the plug, shaking for 15 times at 180 degrees up and down, and recording the foam height H after completion of shaking₀(ii) a After standing for 5minHeight of foam H₅。

TABLE 1 foaming Performance test results for toothpastes prepared in examples 1-4

	H0(mL)	H5(mL)
			Example 1	132	122
Example 2	126	113
			Example 3	164	151
Example 4	186	179
			Example 5	190	180

From the results of the foaming property test of the toothpaste in table 1, it can be seen that the foaming property of the toothpaste can be improved by using carboxymethyl chitosan and silk peptide as stabilizers; and when the carboxymethyl chitosan/silk peptide hydrogel is used as a stabilizer, the stability of the foam is improved on the basis of improving the foaming performance, and the foam is reduced by only 6mL after 5 min. This is probably because the anionic surfactant sodium lauroyl sarcosine in the foaming agent is ionized in the liquid phase environment, and the acid radical ions make the surface of the bubbles negatively charged and repel each other with carboxymethyl chitosan/silk peptide in the liquid phase, so that the bubble interfaces are difficult to approach each other, the liquid phase of the bubbles is prevented from thinning, and the stability of the foam is maintained.

Test example 2 anti-sensitivity test of toothpaste

Screening requirements of subjects participating in anti-allergy testing: the patient is 18-65 years old, has no systemic diseases and is in good physical condition; at least two sensitive sources of tooth origin, resulting from tooth root exposure caused by erosion, abrasion of the neck of the tooth or retraction of the tooth root; during screening and inspection, the quantity of an electron pressure sensitive probe (Yeapple probe) is 10-20 g, and the cold air sensitivity index (Schiff) > 2.

The test groups are:

control group: the commercially available comfortable whitening anti-sensitivity toothpaste for professional repair;

test group 1: the toothpaste prepared in example 3 of the present invention;

test group 2: the toothpaste prepared in example 4 of the present invention.

A total of 75 subjects were enrolled in the trial, who were asked to brush their teeth every morning and evening over 8 weeks, during which time the anti-tooth sensitivity drugs could not be used, and finally 72 subjects completed the trial, each data being an average of the results of the test in this group. The results are shown in Table 2.

TABLE 2 anti-sensitivity testing of toothpastes

From the results in table 2, it can be seen that the anti-sensitivity performance of the toothpastes of example 3 and example 4 prepared by the present invention is similar to that of the commercial toothpaste, and the anti-dentin sensitivity effect of example 4 is the best, probably because potassium ions in the toothpaste formulation can enter dentinal tubules to reduce the permeability of dentin and have affinity with nerve endings, improve the transmission of nerve impulses and relieve the pain of teeth; strontium chloride can react with calcium carbonate in dentin to generate strontium carbonate, and can react with hydroxyapatite to generate hydroxyl strontium apatite to block open tubule of dentin. The carboxymethyl chitosan/silk peptide hydrogel as the stabilizer has coordination function and space network structure capable of dispersing anti-allergic matter properly, and has also anti-inflammatory, antioxidant and high moisture maintaining performance. These factors work together to improve the anti-sensitivity properties of the toothpaste.

Test example 3 whitening and plaque removal test of toothpaste

The screening requirements of the subjects participating in tooth whitening and plaque removal are as follows: the patient is 18-65 years old, has no systemic diseases and is in good physical condition; there are more than 20 natural teeth, and the teeth have extrinsic stains.

The test groups are:

control group: the commercially available comfortable whitening anti-sensitivity toothpaste for professional repair;

test group 1: the toothpaste prepared in example 3 of the present invention;

test group 2: the toothpaste prepared in example 4 of the present invention.

A total of 72 subjects were enrolled in the whitening and plaque removal trial, requiring the subjects to brush their teeth in the morning and evening over 8 weeks, during which time no other tooth whitening substance was used, and finally 70 subjects completed the trial, each data being an average of the results of the test in that group. The results are shown in Table 3.

TABLE 3 whitening and plaque removal test results for toothpaste

From the results in table 3, it can be seen that the whitening and plaque removing performance of the toothpaste prepared in example 3 of the present invention is similar to that of the commercially available toothpaste, while the whitening and plaque removing performance of example 4 is significantly stronger than that of example 3. It is possible that the abrasive particles are harder than the plaque and physically break down the plaque during brushing, and the broken down plaque is broken down into smaller particles during brushing abrasion and is removed from the tooth surface by emulsification of the foaming agent. Example 4 the carboxymethyl chitosan/silk peptide hydrogel used enhanced the emulsifying action of the foaming agent, facilitating the detachment of plaque from the tooth surface; the whitening substance sodium pyrophosphate is easy to hydrolyze, and the network structure of the carboxymethyl chitosan/silk peptide hydrogel can stabilize the sodium pyrophosphate and delay the inactivation of the sodium pyrophosphate; meanwhile, the complexation of the carboxymethyl chitosan/silk peptide hydrogel can also make the sodium pyrophosphate have stronger effect on dental plaque. These factors work together to provide the best whitening performance of the toothpaste prepared in example 4.

Test example 4 evaluation of toothpaste stability

Storing the toothpaste to be tested at 5 deg.C and humidity of 40% for 30 days; storing at 25 deg.C and humidity of 40% for 30 days; storing at 40 deg.C and humidity of 40% for 30 days. The tube was then opened and evaluated for the separation of the liquid components from the toothpaste as follows.

Evaluation criteria for toothpaste stability:

the stability is excellent: no separation of liquid at all was visible

The stability is good: slight separation of the liquid

Poor stability: separation of the liquid is clearly seen

TABLE 4 toothpaste stability

	Stability of
		Example 4	Superior food
Comparative example 1	Difference (D)
		Example 5	Superior food

As can be seen from table 4, the propolis anti-allergy toothpaste of comparative example 1, to which the ethanol-extracted propolis extract is added, easily destroys the internal structure of the gel in the toothpaste, resulting in deterioration of the stability of the paste. According to the invention, the anion graft modified chitosan is prepared by further modifying the chitosan serving as the stabilizer, so that the problem of stability of the toothpaste can be effectively improved.

Claims (10)

1. The propolis anti-allergy toothpaste is characterized in that: comprises propolis extract.

2. The propolis antiallergic toothpaste as claimed in claim 1, wherein: the propolis whitening cream comprises 5-10 parts by weight of a propolis extract, 5-10 parts by weight of an anti-allergy agent, 2-5 parts by weight of a stabilizer, 2-5 parts by weight of a whitening agent, 0.5-1 part by weight of a sweetening agent, 1-3 parts by weight of a remineralizing agent, 15-25 parts by weight of a friction agent, 40-60 parts by weight of a humectant, 0.1-2 parts by weight of a thickener, 1-2 parts by weight of a foaming agent, 0.1-2 parts by weight of a perfume and 10-25 parts by weight of water; the stabilizer is at least one of carboxymethyl chitosan, silk peptide, carboxymethyl chitosan/silk peptide hydrogel and anion graft modified chitosan.

3. The propolis antiallergic toothpaste as claimed in claim 2, wherein the propolis extract is prepared by the method comprising: mixing propolis and ethanol water solution uniformly, oscillating and leaching at room temperature, filtering to remove beeswax, and freeze drying to obtain the propolis extract.

4. The propolis antiallergic toothpaste as claimed in claim 2, wherein: the anti-allergic agent consists of potassium nitrate and strontium chloride; the whitening agent is at least one of sodium pyrophosphate, sodium phytate, titanium dioxide, perlite powder and zinc oxide.

5. The propolis antiallergic toothpaste as claimed in claim 2, wherein: the sweetening agent is at least one of stevioside, saccharin sodium, xylitol, sucralose and dipotassium glycyrrhizinate; the remineralizing agent is hydroxyapatite.

6. The propolis antiallergic toothpaste as claimed in claim 2, wherein: the friction agent is at least one of hydrated silicon dioxide, calcium hydrophosphate, calcium carbonate and aluminum hydroxide; the humectant is at least one of glycerol, sorbitol, propylene glycol, diethylene glycol and ethylene glycol; the thickening agent is at least one of sodium hydroxymethyl cellulose, sodium hydroxyethyl cellulose, nonionic guar gum, xanthan gum, carrageenan and sodium alginate.

7. The propolis antiallergic toothpaste as claimed in claim 2, wherein: the foaming agent is at least one of sodium dodecyl sulfate, sodium lauroyl sarcosinate, sodium lauroyl methyl taurate, sodium lauryl sulfate, cocamidopropyl betaine and sodium cocoyl glycinate; the perfume is at least one of menthol, oleum Menthae Dementholatum, oleum Eucalypti, sweet orange oil, and lemon oil.

8. The propolis antiallergic toothpaste as claimed in claim 2, wherein the carboxymethyl chitosan/silk peptide hydrogel is prepared by a method comprising: dissolving carboxymethyl chitosan and silk peptide in water to form a solution a; dissolving genipin in water to form a solution b; and mixing the solution a and the solution b for crosslinking reaction for 24-36 h, washing with water for three times, and freeze-drying at-55 to-45 ℃ for 24-36 h to obtain the carboxymethyl chitosan/silk peptide composite hydrogel.

9. The propolis antiallergic toothpaste as claimed in claim 2, wherein the anion graft-modified chitosan is prepared by adding chitosan to distilled water, stirring and dispersing uniformly; dropwise adding glacial acetic acid, stirring and mixing uniformly; adding acrylamide and 2-acrylamido-2-methyl-1-propanesulfonic acid, and stirring and mixing uniformly; dropwise adding ammonium ceric nitrate aqueous solution under nitrogen atmosphere, stirring and mixing uniformly, standing for 1-3 h at 20-40 ℃, then aging for 10-24 h at room temperature, centrifuging to take out lower-layer gel, washing with ethanol, freeze-drying, and grinding into powder to obtain the anion graft modified chitosan.

10. The method for preparing the propolis antiallergic toothpaste as claimed in any one of claims 2 to 9, which comprises the steps of:

s1, weighing the raw materials according to the formula; dissolving an anti-allergic agent, a stabilizing agent, a whitening agent and a sweetening agent into partial water under stirring at 50-100 r/min to form a solution I;

s2, mixing the remineralizing agent, the friction agent and the thickening agent under stirring at 50-100 r/min to form a mixed system II;

s3, mixing the humectant and the rest water under stirring at 50-100 r/min to form a system III, adding the solution I obtained in the step S1 into the system III, vacuumizing to-0.05-0.1 Mpa, and stirring at 50-100 r/min to form a system IV; pumping the mixed system II into the system IV, and homogenizing for 10-20 min at the rotation speed of 8000-10000 r/min and the vacuum degree of-0.05-0.085 Mpa to obtain a system V;

s4, absorbing the foaming agent and the spice into the system V of the step S3, and homogenizing for 10-20 min at the vacuum degree of-0.05-0.085 Mpa and the rotating speed of 8000-10000 r/min; then degassing until the vacuum degree is-0.95 to-0.1 Mpa, and obtaining the propolis anti-allergy toothpaste.